4-Trimethylsilanylmethyl-cyclohex-3-enecarboxylic acid methyl ester | 71092-48-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4-Trimethylsilanylmethyl-cyclohex-3-enecarboxylic acid methyl ester
• 英文别名: Methyl 4-trimethylsilylmethyl-3-cyclohexenecarboxylate；methyl 4-(trimethylsilylmethyl)cyclohex-3-ene-1-carboxylate
• CAS: 71092-48-3
• 化学式: C₁₂H₂₂O₂Si
• 分子量: 226.391
• InChiKey: DBBWPGOLVKGOEO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Trimethylsilanylmethyl-cyclohex-3-enecarboxylic acid methyl ester 在 乙酰氯 作用下， 以 甲醇 、 乙醚 为溶剂， 生成 alpha,alpha-二甲基-4-亚甲基环己烷甲醇
  参考文献：
  名称：

  Isoprene synthons. Silicon- and tin-mediated terpene synthesis

  摘要：

  DOI：

  10.1021/ja00506a034
• 作为产物：
  描述：

  三甲基(2-亚甲基丁-3-烯基)硅烷 、 丙烯酸甲酯（MA） 在 二甲基氯化铝 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以88%的产率得到4-Trimethylsilanylmethyl-cyclohex-3-enecarboxylic acid methyl ester
  参考文献：
  名称：

  Tandem Transformations Involving Allylic Silanes. 2. Highly Diastereoselective Substitutions Involving [(Trialkylsilyl)methyl]cyclohexene Derivatives with Aldehydes. Synthetic Studies on the Problem of Lewis Acid-Promoted Protodesilylation and Enolization

  摘要：

  Diels-Alder cycloaddition of 2-[(trialkylsilyl)methyl]-1,3-butadienes with a variety of dienophiles and substitution reactions between these allylsilane-containing adducts and aldehyde or acid chloride electrophiles have been combined into ''tandem sequential reactions.'' These tandem sequences proceed with equal or greater yield (50-80%) than the reactions performed separately with no decrease in regio- or stereoselectivity. The sequence produces cyclic compounds with three or four stereogenic centers with good to excellent diastereoselectivity from three simple, noncyclic, and achiral reaction partners. Unprecedented levels of diastereoselectivity (de > 93%) have been achieved in allylic substitution reactions involving substituted [(trialkylsilyl)methyl]cyclohexene derivatives with aldehyde electrophiles. During the course of these studies, protodesilylation of allylsilanes has been investigated in detail, and a cocatalyst system of TiCl4 and Me2AlCl has been developed that has eliminated silicon loss in the substitution reactions studied. Lewis acid-promoted enolization of ester and ketone substrates with chiral centers adjacent to the carbonyl moiety has been studied also. It has been shown that this event in our studies occurs primarily during catalyst quench. This isomerization is prevented by quenching the catalyst with a Lewis base, such as methanol or triethylamine, prior to aqueous workup.

  DOI：

  10.1021/jo970821v

文献信息

• Chemistry of organosilicon compounds—165
  作者：Hideki sakurai、Akira Hosomi、Masaki Saito、Koshi Sasaki、Hirokazu Iguchi、Jun-Ichi Sasaki、Yoshitaka Araki

  DOI：10.1016/s0040-4020(01)88587-2

  日期：1983.1

  of synthetically useful reactions of 2-trimethylsilylmethyl-1,3-butadiene (7) are discussed. Reactions of 7 with acid chlorides, aldehydes, ketones and acetals activated by a Lewis acid give isoprenylated compounds, while 7 undergoes the Diels-Alder reaction with dienophiles. High regiospecificity of the reaction qualifies 7 for a versatile building block of terpene synthesis.

  讨论了2-三甲基甲硅烷基甲基-1,3-丁二烯（7）的两种合成上有用的反应。7与路易斯酸活化的酰基氯，醛，酮和乙缩醛的反应生成异戊二烯基化的化合物，而7与亲二烯体进行Diels-Alder反应。该反应的高区域特异性使7成为萜烯合成的通用组成部分。
• Highly regioselective diels-alder reactions of 2-trimethylsilylmethyl- 1,3-butadiene catalyzed by a lewis acid and applications to syntheses of terpenes
  作者：Akira Hosomi、Hirokazu Iguchi、Jun-ichi Sasaki、Hideki Sakurai

  DOI：10.1016/s0040-4039(00)86886-0

  日期：1982.1

  2-Trimethylsilylmethyl-1,3-butadiene undergoes highly regioselective Diels-Alder reactions with dienophiles such as acrolein and methyl vinyl ketone catalyzed by aluminum chloride in which the “para” isomers are obtained almost exclusively. The adducts are converted readily to a variety of naturally occurring mono and sesquiterpenes.

  2-三甲基甲硅烷基甲基-1,3-丁二烯与亲二烯（如丙烯醛和甲基乙烯基酮）通过氯化铝催化发生高度区域选择性的Diels-Alder反应，其中几乎完全获得“对”异构体。加合物易于转化为各种天然存在的单倍体和倍半萜。
• Fluorination process
  申请人：Gouverneur Veronique

  公开号：US20070142632A1

  公开（公告）日：2007-06-21

  Compounds of formula (II), (IIIa) or (IIIb) (variables are described in the specification) are prepared by fluorination of β,γ-unsaturated alkyl silanes. These compounds are useful as building blocks in the pharmaceutical industry.

  根据说明书中描述的变量，通过对β,γ-不饱和烷基硅烷进行氟化制备出式（II）、（IIIa）或（IIIb）的化合物。这些化合物在制药工业中作为构建模块非常有用。
• Highly regioselective diels-alder reactions of 2-trimethylsilylmethyl- and 2-trimethylstannylmethyl-1,3-butadiene
  作者：Akira Hosomi、Masaki Saito、Hideki Sakurai

  DOI：10.1016/s0040-4039(01)85471-x

  日期：1980.1
• Noncascade Tandem Transformations Involving Allylic Silanes. 1. Pericyclic and Ionic Reactions Combined into “One-Pot” Sequences
  作者：Michael G. Organ、Derick D. Winkle

  DOI：10.1021/jo962025f

  日期：1997.3.1